Novel protocols for acquiring quantitative (13)C NMR spectra of lignins have been developed using the internal reference compounds 1,3,5-trioxane and pentafluorobenzene. Trioxane offers a convenient internal standard for collecting inverse gated proton decoupled (13)C NMR spectra for lignins, whereas pentafluorobenzene can be used to provide information on the amount of methine carbon using the DEPT experiment. In each case, the internal reference compounds provide single, un-overlapped sharp signals in the middle of the spectral region, permitting facile integration. These integrals could be used to determine the amounts of different structural features of lignins, expressed in absolute units of millimoles per gram. The optimum parameters for these experiments were validated for a variety of spectrometer platforms, and standard errors were determined for different spectral areas using lignin model compounds and "standard" lignins. In addition, the data derived for the International Round Robin "standard" lignins showed good agreement with the data from quantitative (31)P NMR spectroscopy and published data, obtained by independent laboratories using independent methods of analysis.

Summary Milled wood lignins isolated from genetically modified poplar trees were studied by quantitative 31P NMR spectroscopy, in combination with thioacidolysis and mild alkaline hydrolysis. The genetic transformation of the trees included down regulation of CAD and COMT enzyme activities. These analyses confirmed that moderate CAD down-regulation does not substantially alter lignin structure. In contrast, severe CAD deficiency alters the lignin structure more profoundly by decreasing the syringyl/guaiacyl ratio and increasing the degree of condensation of the lignin. The most severe alterations were observed in the lignins from the COMT-transformed lines.

Softwood kraft pulp was subjected to a laboratory one- and three-stage oxygen delignification process. Pulp and liquor samples were collected at different stages of the process with particular attention being paid to the early and late stages. A novel residual lignin isolation method extracted about 65% of the oxidized residual lignins at a purity exceeding 90%. Using this methodology coupled to quantitative 31P NMR, 13C NMR, 2D heteronuclear (HMQC) NMR spectroscopic and analytical pyrolysis techniques allowed a thorough characterization of the residual and solubilized lignin fractions at the various stages of the process. Our conclusions do not point to a single factor as being responsible for the limits confronting oxygen delignification. Amongst the major factors impeding the effectiveness of oxygen delignification are: (i) the accumulation of relatively inert 5,5' biphenyl structures originally present in kraft lignin from dibenzodioxocin ring opening reactions; and (ii) the accumulation of considerably less reactive p-hydroxyphenyl structures. Detailed quantitative information was obtained and discussed in relation to the presence and role of these unreactive phenolic fractions on the residual oxidized lignins. As such we arrived at important conclusions as to why and how these structures remain and accumulate on the fiber. In addition, issues related to the profiles of the total phenolic hydroxyl content of the residual lignins and the remaining arylglycerol β-O-4 structures are discussed.Key words: analytical pyrolysis, biphenyl structures, HMQC, NMR, oxidation mechanism, oxygen delignification, p-hydroxyphenyl moieties, quantitative 13C NMR, quantitative 31P NMR, residual lignin, solubilized lignin, total phenolic hydroxyls.

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In an effort to augment the efficiency of an oxygen delignification stage, we examined the effectiveness of various heterocyclic aromatic nitrogen compounds as possible activators of such a stage. It was shown that a variety of such compounds may act as activators in the presence of hydrogen peroxide, improving the delignification efficiency of oxygen delignification. Among the group of activators examined, 1,10-phenanthroline was found to be the most potent. Injecting the activator in the middle of the delignification stage (simulating a two-stage process) was shown to provide most of the benefits. The optimum injection time was found to at 30 min from the onset of the delignification. At the optimal charge of 1,10-phenanthroline (0.3%), the delignification was improved by 18%. While the presence of copper ions was found to further improve the efficiency of the activating system, this was accompanied by an extensive carbohydrate degradation.